WO1999012888A1 - Method for producing aryloligoamines - Google Patents

Abstract

The invention relates to a method for producing aryloligoamines, characterised in that an amine is reacted with an activated aromatic and a base within a temperature range from 0 and 150 DEG C in the presence of a palladium constituent and a phosphane ligand. The inventive method is easy to carry out and produces high yields.

Description

description

Process for the preparation of aryl oligoamines

Aryl and heteroaryl derivatives, which have several amine units (hereinafter aryl oligoamines), have long been used in various applications. For example, they can be used as hole conductors in xerography (see, for example, PM Borsenberger, DS Weiss, Organic Photoreceptors for Imaging Systems, Marcel Dekker, Inc.), in organic electroluminescent devices (see, for example, JJ Kido, Bull. Electrochem. 1994, 10, 1-13; DE-A-197 11 714) and dye-sensitized photovoltaic cells (see, for example, DE-A 197 1 1 714).

Derivatives of spirobifluorene, among others, have proven to be particularly interesting (see e.g. DE-A 197 11714).

Aryloligoamines are generally built up via variants of the Ullmann reaction (J. March. Adv. Org. Chem. 4th Ed., P. 665, John Wiley & Sons, New York 1992). For example, the representation of 4,4 ', 4 "tris (N, N-diphenylamino) triphenylamine (Shirota et al., Chem. Lat. 1989, 1 145-1 148) and tris

(4-phenoxazin-10-yl-phenyl) amine (Higuchi et al., Mol.Cryst.üq.Cryst. 1994, 242, 127-134) via this route. For the production of hole conductors based on spiro compounds such as N, N, ^{N, N,} N ', N ", ^N", N ^{"-Octaphenylspiro-9,9'-bifluoren-2,2',} 7 , 7'-tetramine (Salbeck et al., Book of Abstracts, 213 ^th ACS National Meeting, San Francisco 1997, 199) describes this reaction.

In general, the production of aryl oligoamines is more difficult than that of aryl monoamines. For example, known that Ullmann reactions can be carried out under optimal conditions with a yield of about 80%. Applying this to a tri or

Tetra coupling reaction arrives, so theoretically only 51 or 41% yield, which on the one hand affects the economy and on the other hand makes cleaning the products more difficult.

It has now surprisingly been found that aryloligoamines can be prepared simply and in good yields by directly coupling a primary or secondary amine with an activated aromatic in the presence of a base, a palladium component and a phosphine ligand.

A similar process is known from US Pat. No. 5,576,460, but it is only described there for the preparation of aryl monoamines.

In addition, a yield of only 75% is obtained in the only example, which leads the person skilled in the art to conclude that such a method for building up aryloligoamines is less suitable than the Ullmann reaction. The invention therefore relates to a process for the preparation of aryloligoamines, characterized in that an amine with an activated

Aromatics and a base in a temperature range from 0 to 150 ° C in the presence of a palladium component and a phosphine ligand.

For the purposes of the invention, aryloligoamine means a compound which contains at least two amine units bonded to aromatic groups.

Preferred starting compounds are activated aromatics of the general formula (I),

(R) _n -A- (X) _m (I)

where the symbols and indices have the following meaning:

A is an aromatic and / or heteroaromatic radical with 2 to 200 carbon atoms, which may contain several aromatic and / or heteroaromatic groups, such groups then condensing (for example Anthracene, triphenylene) or uncondensed (for example biphenyl, terphenyl, 1, 3,5-triphenylbenzene);

R is the same or different NO ₂ , CN, F, an unbranched or branched alkyl group having 1 to 22 C atoms, one or more CH ₂ groups being represented by -O-, -S-, -CO-, -O-CO -, -CO-O-, -O-CO-O-, -CR ¹ = CR ² , -C _≡ C-, SiR ³ R ⁴ , C ₄ -C ₁₀ aryldiyl, C ₄ -C ₁₀ heteroaryldiyl, Cyclohexylene, -NR ⁵ - can be replaced, wherein heteroatoms must not be directly linked to one another, and one or more H atoms can be replaced by F, Cl, Br;

R \ R ² are identical or different H, CN, C _r C ₁₂ alkyl, C ₄ -C ₁₀ aryl;

R ³ , R ⁴ are identical or different C _r C ₁₂ alkyl, C ₄ -C ₁₀ aryl;

R ⁵ is CC ₁₂ alkyl, C ₄ -C ₁₀ aryl;

X is Cl, Br, I, mesylate, tosylate or C ₁ -C ₁₂ perfluoroalkyl sulfonate;

m is a natural number, where 2 <m <y;

n is a natural number, where 0 <n <y-m;

y is the number of free valences on the base body A;

The symbols and indices in the formula (I) preferably have the following meanings:

R is the same or different NO ₂ , CN, F, an unbranched or branched alkyl group with 1 to 22 C atoms.

X Cl, Br, I, tosylate; m 3 <m <y;

The symbols and indices in the formula (I) particularly preferably have the following meanings:

A is benzene, naphthalene, anthracene, pyrene, triphenylene, biphenyl, fluorene, terphenyl, 1, 3,5-triphenylbenzene, spiro-9,9'-bifluorene, 2,2 ', 7,7'-tetraphenylspiro-9,9 '-bifluoren, 2,2', 7,7'-tetra (4'-biphenylyl) spiro-9,9'-biphenyl, ^{2,4,7,2'4, 7'-Hexaphenylspiro-9,9,} -bifluoren and ^2,4,7,2, 4 ', 7'-hexa (4'-biphenylyl) spiro-9,9'-bifluorene or other oligophenylene- substituted derivative of the spiro-9,9'-bifluorens;

R is the same or different NO ₂ , CN, F, an unbranched or branched alkyl group with 1 to 22 C atoms.

X is Br, I;

m is 4, 5 or 6 and

n is 0, 1, 2, 3, 4, 5, 6.

Particularly preferred activated aromatics of the formula (I) are those of the formula (Ia)

wobei X gleich oder verschieden, Br, I oder H und k,l,p,q,r,s 0, 1 , 2, 3, 4 bedeuten, mit der Maßgabe, daß mindestens zwei, vorzugsweise mindestens vier, der Reste X Br oder I sind.

where X is the same or different, Br, I or H and k, l, p, q, r, s 0, 1, 2, 3, 4, with the proviso that at least two, preferably at least four, of the radicals X Br or I are.

Preferred amine components are those of the formula (II)

where the symbols have the following meanings:

R ⁷ , R ⁸ are identical or different a) H; b) a straight-chain, branched or cyclic alkyl group with 1 to 22 carbon atoms, one or more CH ₂ groups being replaced by -O-, -S-, -CO-, -O- CO-, -CO-O-, -O-CO-O-, -CR ¹ = CR ² , -C≡C-, SiR ³ R ⁴ , C ₄ -C ₁₀ aryldiyl, C ₄ -C ₁₀ heteroaryldiyl , Cyclohexylene, -NR ⁵ -, where heteroatoms must not be directly linked to one another, and where one or more H atoms can be replaced by F, Cl, Br; wherein R ¹ to R ^{5 have} the meanings given in the formula (I); c) a C ₄ -C ₁₂ aryl or heteroaryl group which can be substituted by one or more radicals R, where R has the same or different meanings given in the formula (I).

End products of the process according to the invention and their preferences result from the starting materials and their preferences.

The starting materials of the process are known in principle and are either commercially available or according to known methods known to those skilled in the art, such as, for example, in Houben-Weyl, Methods of Organic Chemistry, Georg Thieme

Verlag, Stuttgart, can be produced.

The ratio of the starting materials is not critical and can therefore be varied within a wide range, a ratio of activated group to amine of 1: 0.8 to 2, particularly preferably 1: 1 to 1.5, is preferred.

According to the invention, the starting compounds, amine and activated aromatic, are converted into an aryloligoamine in a coupling reaction.

To carry out the reaction, the amine, the activated aromatic, a base and catalytic amounts of a phosphine ligand are contained

Palladium catalyst or a palladium salt and a phosphane are taken up in a solvent and at a temperature of 0 ° C to 150 ° C, preferably at 30 ° C to 140 ° C, particularly preferably at 50 ° C to 120 ° C, particularly preferably at 80 ° C to 120 ° C for a period of 1 h to 200 h, preferably 5 h to 100 h, particularly preferably 10 h to 80 h, implemented. The

Working up is carried out according to methods known per se and familiar to the person skilled in the art, for example by hydrolysis, stirring, phase separation and removal of the solvent. The palladium component is also preferably removed by stirring with a complexing agent. Cyanide, thiocyanate and others are suitable here. The crude product can then according to the person skilled in the art and the particular

Appropriate methods, e.g. by recrystallization, distillation, sublimation, zone melting, melt crystallization or chromatography.

The process according to the invention is generally carried out in a solvent, an excess of the base or of a starting material, preferably the amine component, also being able to serve as such a solvent.

The use of one or more organic solvents or a mixture of water and one or more organic solvents is preferred, in which case at least one of the organic solvents should preferably be water-insoluble.

Preferred organic solvents are ethers, e.g. B. diethyl ether, dimethoxymethane, diethylene glycol dimethyl ether, tetrahydrofuran, dioxane, dioxolane, diisopropyl ether, tert-butyl methyl ether, hydrocarbons, e.g. B. hexane, iso¬

Hexane, heptane, cyclohexane, toluene, xylene, alcohols, e.g. B. methanol, ethanol, 1-propanol, 2-propanol, ethylene glycol, 1-butanol, 2-butanol, tert-butanol, ketones, e.g. B. acetone, ethyl methyl ketone, iso-butyl methyl ketone, amides, e.g. Dimethylformamide, dimethylacetamide, N-methylpyrrolidone, nitriles, e.g. Acetonitrile, propionitrile, butyronitrile, and mixtures thereof.

Particularly preferred organic solvents are ethers, such as dimethoxyethane, diethylene glycol dimethyl ether, tetrahydrofuran, dioxane, diisopropyl ether, hydrocarbons, such as hexane, heptane, cyclohexane, toluene, xylene, alcohols, such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol,

Ethylene glycol, ketones such as methyl ethyl ketone, iso-butyl methyl ketone, amides such as Dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and mixtures thereof.

Very particularly preferred organic solvents are ethers, e.g. B. dimethoxyethane, tetrahydrofuran, dioxane, hydrocarbons, e.g. B. cyclohexane,

Toluene, xylene, alcohols, e.g. As ethanol, 1-propanol, 2-propanol, 1-butanol, tert-butanol and mixtures thereof.

Examples of the use of water and organic solvents are mixtures of water and toluene and water, toluene and tetrahydrofuran.

Bases which are preferably used in the process according to the invention are alkali and alkaline earth metal hydroxides, alkali and

Alkaline earth metal carbonates, alkali metal hydrogen carbonates, alkali and alkaline earth metal acetates, alkali and alkaline earth metal alcoholates, as well as primary, secondary and tertiary amines.

This means that the amine component used, a corresponding

Provided excess can also act as a base.

Alkali and alkaline earth metal hydroxides, alkali and alkaline earth metal carbonates and alkali and alkaline earth metal alcoholates are particularly preferred.

Alkali metal hydroxides, such as sodium hydroxide and, are particularly preferred

Potassium hydroxide, and alkali and alkaline earth metal alcoholates, such as sodium ethanolate and sodium or potassium tert-butoxide.

In the process according to the invention, the base is preferably present in a proportion of 50 to 500 mol%, particularly preferably 50 to 250 mol%, very particularly preferably 75 to 200 mol%, in particular 90 to 120 mol%, based on the moles present NH, used.

The palladium component contains palladium metal or a palladium (0) or (II)

Connection. Palladium component and phosphine ligand can be used as a complex, for example as the preferred Pd (PPh ₃ ) ₄ , or separately.

Suitable palladium components are, for example, palladium compounds, such as palladium ketonates, palladium acetylacetonates, nitrile palladium halides,

Olefin palladium halides, palladium halides, allyl palladium halides and palladium biscarboxylates, preferably palladium ketonates, palladium acetylacetonates, bis-η ² -olefin palladium dihalides, palladium (II) halides, η ³ -allyl palladium halide dimers and palladium benzodiacid (palladium bisdibarbon) (palladium benzyl dibarbyl) (palladium bisdibidone) (palladium benzodibibone) (palladium benzodibibone) (palladium bisdibarbon) (palladium bisdibarboxylate) (especially palladium benzodibibone) (palladium bisdibarbon) (palladium bisdibarboxylate) (palladium bisdibibone) (palladium bisdibibone) (palladium bisdibarbyl) (palladium bisdibacyl) (particularly preferred ₂ )], Pd (dba) ₂ CHCI ₃ , palladium bisacetylacetonate, bis (benzonitrile) palladium dichloride, PdCI ₂ , Na ₂ PdCI ₄ , dichlorobis (dimethyl sulfoxide) palladium (II), bis (acetonitrile) palladium dichloride, palladium II acetate , Palladium-II-propionate, palladium-II-butanoate and (1c, 5c-cyclooctadiene) palladium dichloride.

Palladium can also serve as a palladium component in metallic form, hereinafter only called palladium, preferably palladium in powdered form or on a support material, for example palladium on activated carbon, palladium on aluminum oxide, palladium on barium carbonate, palladium on barium sulfate, palladium on aluminum silicates, such as montmorillonite, Palladium on SiO ₂ and

Palladium on calcium carbonate, each with a palladium content of 0.5 to 10 wt .-%. Palladium in powdered form, palladium on activated carbon, palladium on barium and / or calcium carbonate and palladium on barium sulfate, in each case with a palladium content of 0.5 to 10% by weight, are particularly preferred. Palladium on activated carbon with a palladium content of is particularly preferred

5 or 10% by weight

In the process according to the invention, the palladium component is used in a proportion of 0.01 to 10 mol%, preferably 0.05 to 5 mol%, particularly preferably 0.1 to 3 mol%, particularly preferably 0.1 to 1.5 Mol%, based on the N-

H groups. Suitable phosphine ligands for the process according to the invention are, for example, trialkylphosphines, tricycloalkylphosphanes, triarylphosphines, where the three substituents on the phosphorus can be the same or different, chiral or achiral and one or more of the ligands can link the phosphorus groups of several phosphines and part of this linkage also includes or can be several metal atoms.

Examples of phosphanes which can be used in the process according to the invention are trimethylphosphine, tributylphosphine, tricyclohexylphosphine, triphenylphosphine, tritolylphosphine, tris (4-dimethylaminophenyl) phosphine, bis (diphenylphosphano) methane, 1,2-bis (diphenylphosphano) ethane, 1,3

Bis (diphenylphosphano) propane and 1, 1'-bis (diphenylphosphano) ferrocene.

Triphenylphosphine, tris (o-tolyl) phosphane, 1,2-bis (diphenylphosphano) ethane, 1,3-bis (diphenylphosphano) propane and 1,1'-bis (diphenylphosphano) ferrocene, especially triphenylphosphane and tris, are very particularly preferred (o-tolyl) phosphine.

Also suitable for the process according to the invention are water-soluble phosphine ligands which contain, for example, sulfonic acid salt and / or sulfonic acid residues and / or carboxylic acid salt and / or carboxylic acid residues and / or phosphonic acid salt and / or phosphonic acid residues and / or phosphonium groups and / or peralkylammonium groups and / or hydroxyl groups and / or Contain polyether groups with a suitable chain length.

Preferred classes of water-soluble phosphine ligands are trialkylphosphines substituted with the above groups, tricycloalkylphosphanes, triarylphosphines,

Dialkylarylphosphanes, alkyldiarylphosphanes and heteroarylphosphines such as tripyridylphosphine and trifurylphosphine, where the three substituents on the phosphorus may be the same or different, chiral or achiral and where one or more of the ligands may link the phosphorus groups of several phosphines and part of this linkage may also be one or more metal atoms can. In the process according to the invention, the phosphine ligand is used in a proportion of 0.1 to 20 mol%, preferably 0.2 to 15 mol%, particularly preferably 0.5 to 10 mol%, particularly preferably 1 to 6 mol%, based on the NH present - Groups.

Mixtures of two or more different phosphine ligands can optionally also be used.

The products of the method according to the invention are e.g. for use in electroluminescent devices, dye-sensitized photovoltaic cells or in xerography, for example as hole conductor materials.

The invention is explained in more detail by the following examples, without wishing to restrict it thereby.

Example 1 :

-Bifluoren Preparation of 2,2 ', 7,7'-tetrakis (N, N-diphenylamino) ^-spiro-9,9'

2.2 ^' , 7.7 ^' tetrabromo-9.9 ^' spirobifluorene (20.86 g, 33 mmol) and diphenylamine (25.38 g, 150 mmol) were placed in toluene (400 ml) and the solution with N ₂ saturated.

Then Pd (OAc) ₂ (311 mg, 1.5 mmol), P (o-tolyl) ₃ (0.913 g, 3 mmol) and the base (NaO'Bu, 20.18 g, 210 mmol) were added. The solution immediately turned dark green. It was stirred under reflux for 72 hours.

After the mixture had cooled to room temperature, NaCN solution was added (about 2 g of NaCN in 200 ml of water) and the mixture was stirred for about 60 min. It was then washed three times with water. The organic phase was dried over Na ₂ SO ₄ and the solvent was then stripped off. Light brown was obtained

Crystals.

These were recrystallized from 100 ml of dioxane and 5 ml of hydrazine hydrate. This process was repeated once. Finally, the crystals obtained were stirred several times with hexane and dried in vacuo at 60 ° C. 19.3 g (59%) of colorless powder were obtained which, according to HPLC, had a purity of greater than 99.7%.

¹ H NMR (CDCI ₃ , NH ₂ NH ₂ * H ₂ O): δ [ppm] = 7.45 (d, 4H, H-4, J = 8 Hz), 7.19 (m, 16 H, H-3 ') , 6.97 (m, 24 H, H-2 \ H-4 '), 6.92 (dd, 4 H, H-3, J, = 2, J ₂ = 8 Hz), 6.69 (d, 4 H,

H-1, J = 2 Hz).

The use of DPPF (bis (diphenylphosphino) ferrocene) as a ligand led to a deterioration in yield (45%; purity:> 99.9%), the use of BINAP (2,2'-bis (diphenylphosphino) -1, 1'-binaphthyl) however, to an easy one

Increased yield (62%; purity:> 99.7%).

Example 2:

-Bifluoren Preparation of 2,2 ', 7,7'-tetrakis (N, N-di-4-methoxy-phenylamino) ^-spiro-9,9'

2,2 ^' , 7,7 ^' tetrabromo-9,9 ^' spirobifluorene (13.9 g, 22 mmol) and 4,4'-dimethoxydiphenylamine (22.98 g, 100 mmol) were dissolved in toluene (250 ml) and the solution saturated with N ₂ . The solution turned brown. Then Pd (OAc) ₂ (223 mg, 1 mmol) and P (o-tolyl) ₃ (608 mg, 2 mmol) were added. NaO'Bu (13.5 g, 140 mmol) was added dropwise as a solution in dioxane (in 150 ml). The solution slowly turned dark brown when added dropwise. The solution was stirred under reflux under protective gas for 72 hours.

After cooling to room temperature, hydrolysis was carried out with H ₂ O, the water phase was separated off, stirred with NaCN solution (3 g of NaCN in 300 ml of water) for 2 hours and then the water phase was separated off again. The organic phase was filtered and the solvent was removed. A black oil was obtained which solidified over time. It was dissolved hot in 50 ml of dioxane, mixed with 50 ml of ethanol in the heat and cooled with stirring. A yellow-green solid precipitated out. This was suctioned off and washed several times with small portions (2 ml each) of dioxane; until the color was light yellow. The mixture was then recrystallized again from very little dioxane (addition of a few drops of hydrazine hydrate). 13.9 g (52%) of almost colorless powder were obtained, which had a purity of 99% according to ¹ H-NMR.

¹ H NMR (CDCI ₃ , NH ₂ NH ₂ * H ₂ O): δ [ppm] = 7.36 (d, 4H, H-4, J = 8 Hz), 6.90 + 6.75 (AA'BB ', each 16 H , H-2 ', H-3 "), 6.79 (dd, 4 H, H-3, J, = 2, J ₂ = 8 Hz), 6.55 (d, 4 H, H-1, J = 2 Hz ), 3.77 (s, 24 H, OMe).

Example 3:

Preparation of 2,2 ', 7,7'-tetrakis (N-phenothiazinyl) -spiro-9,9 ^' -bifluorene

The reaction was carried out analogously to Example 2. In the workup, the solid formed was filtered off with suction after stirring with NaCN solution. The solid obtained was first boiled for about 1 hour with acetone: water: hydrazine hydrate (70: 15: 3) and finally recrystallized from chloroform: ethanol (1: 1). The pure product (according to ¹ H-NMR purity> 99%) was obtained as a colorless powder: 47% yield.

¹ H NMR (CDCI ₃ , NH ₂ NH ₂ * H ₂ O): δ [ppm] = 8.06 (d, 4H, H-4, J = 8 Hz), 7.43 (dd, 4 H, H-3, J , = 2, J ₂ = 8 Hz), 7.08 (d, 4 H, H-1, J = 2 Hz), 6.96 (dd, 4 H, H-4 ', J, = 1.5, J ₂ = 7.5 Hz ), 6.71 (dt, 4 H, H-3 ', J, = 1.2, J ₂ = 7.5 Hz), 6.47 (ddd, 4 H, H-2', J, = 1.5, J ₂ = 7.3 Hz, J ₃ = 8.3 Hz), 5.98 (dd, 4 H, H-1 \ J, = 1.0, J ₂ = 8.3 Hz).

Example 4:

-Bifluoren Preparation of 2,2 ', 7,7'-tetrakis (N, N-di-4-methylphenylamino) ^-spiro-9,9'

2,2 ^' , 7,7 ^' tetrabromo-9,9 ^' spirobifluorene and 4,4'-dimethyldiphenylamine were reacted analogously to Example 2. The processing was also carried out analogously. After drying, 51% of the product was obtained (purity:> 99.5% by NMR).

¹ H NMR (CDCI ₃ , NH ₂ NH ₂ * H ₂ O): δ [ppm] = 7.39 (d, 4H, H-4, J = 8 Hz), 6.99 + 6.88 (AA'BB ', each 16 H , H-2 ', H-3'), 6.85 (dd, 4 H, H-3, J ₁ = 2, J ₂ = 8 Hz), 6.66 (d, 4 H,

H-1, J = 2 Hz), 2.29 (s, 24 H, Me). Example 5:

Preparation of 2,2 ', 7,7'-tetrakis (N-phenyl-N- (3-methylphenyl) amino) ^-spiro-9,9' - bifluorene

2,2 ', 7,7'-tetrabromo-9,9 ^' -spirobifluorene and 3-methyldiphenylamine were analogous to

Example 1 implemented. DPPF was used as the ligand. The workup was also carried out analogously, but the product proved to be significantly more difficult to clean. The mixture was first filtered twice over a silica gel column and then initially recrystallized from ethyl acetate / methanol (2: 1), then repeatedly from dioxane. After drying, 26% product was obtained (purity:> 99.9% according to HPLC).

¹ H NMR (CDCI ₃ , NH ₂ NH ₂ ^* H ₂ O): δ [ppm] = 7.43 (d, 4H, H-4, J = 8 Hz), 7.18 + 6.97 + 6.94 (AA'BB'C, 8 + 8 + 4 H, H-3 ', H-2', H-4 '), 7.08 (t, 4 H, H-5 ", J = 7 Hz), 6.89 (dd, 4 H, H- 3, J, = 2, J ₂ = 8 Hz), 6.84 (s (br), 4 H, H-2 "), 6.78 (m, 8 H, H-4", H-6 "), 6.68 ( d, 4 H, H-1, J = 2 Hz), 2.22 (s, 12 H, Me).

Example 6:

-Bifluoren Preparation of 2,2 ', 7,7'-tetrakis (N, N-di-4-biphenylamino) ^-spiro-9,9'

2,2 ^' , 7,7 ^' tetrabromo-9,9 ^' spirobifluorene and 4,4'-biphenylamine were analogous to

Example 2 implemented. The processing was also carried out analogously. After drying, 31% of product was obtained (purity:> 99.7% according to HPLC).

¹ H NMR (CDCI ₃ , NH ₂ NH ₂ Η ₂ O): δ [ppm] = 7.53 (d, 4H, H-4, J = 8 Hz), 7.51 + 7.37 + 7.28 (AA'BB'C, 16 + 16 + 8 H, H-2 ", H-3", H-4 "), 7.42 + 7.12 (AA'BB ', each 16 H,

H-2 ', H-3'), 7.03 (dd, 4 H, H-3, J, = 2, J ₂ = 8 Hz), 6.86 (d, 4 H, H-1, J = 2 Hz) . Example 7:

Preparation of 2,2 ', 7,7'-tetrakis (N-phenyl-N- (2-naphthyl) amino) -spiro-9,9'-bifluorene

2,2 ', 7,7 ^' tetrabromo-9,9'-spirobifluorene and 2-naphthylphenylamine were reacted analogously to Example 5. The workup was also carried out analogously, the product also proved to be difficult to clean. The mixture was first filtered twice over a silica gel column and then recrystallized several times from dioxane / methanol. After drying, 35% product was obtained (purity:> 99.7% according to HPLC).

¹ H NMR (CDCI ₃ , NH ₂ NH ₂ * H ₂ O): δ [ppm] = 7.75 (dd, 4 H, H-5 _NP , J, = 2, J ₂ = 7 Hz),

= 2, J₂ = 8.8 Hz), 6.95 (dd, 4 H, H-3, J, = 2, J₂ = 8 Hz), 6.76 (d, 4 H, H-1 , J = 2 Hz). 7.67 (d, 4 H, H-4 _NP , J = 9 Hz), 7.53 (dd, 4 H, H-8 _NP , J, = 2, J ₂ = 7.5 Hz), 7.44 (d, 4H, H- 4, J = 8 Hz), 7.35 (m, 12 H, H-1 _NP , H-6 _NP , H-7 _NP ), 7.23 + 7.08 + 7.03 (AA'BB'C, 8 + 8 + 4 H, H-3 _PH , H-2 _PH , H-4 _PH ), 7.19 (dd, 4 H, H-3 _NP ,

= 2, J ₂ = 8.8 Hz), 6.95 (dd, 4 H, H-3, J, = 2, J ₂ = 8 Hz), 6.76 (d, 4 H, H-1, J = 2 Hz).

Claims

claims 1. A process for the preparation of aryl oligoamines, characterized in that an amine is reacted with an activated aromatic and a base in a temperature range from 0 to 150 ° C in the presence of a palladium component and a phosphine ligand. 2. The method according to claim 1, characterized in that one uses an activated aromatic of the general formula (I), (R) _n -A- (X) _m (I) where the symbols and indices have the following meaning: A is an aromatic and / or heteroaromatic radical with 2 to 200 C- Atoms which can contain several aromatic and / or heteroaromatic groups, such groups then being condensed; R is the same or different NO ₂ , CN, F, an unbranched or branched alkyl group having 1 to 22 C atoms, one or more CH ₂ groups being represented by -O-, -S-, -CO-, -O-CO -, -CO-O-, -O-CO-O-, -CR ¹ = CR ² , -C≡C-, SiR ³ R ⁴ , C ₄ -C ₁₀ aryldiyl, C ₄ -C ₁₀ heteroaryldiyl, Cyclohexylene, -NR ⁵ - can be replaced, wherein heteroatoms must not be directly linked to one another, and one or more H atoms can be replaced by F, Cl, Br; R \ R ² are identical or different H, CN, C _r C ₁₂ alkyl, C ₄ -C ₁₀ aryl; R ³ , R ⁴ are identical or different CC ₁₂ alkyl, C ₄ -C ₁₀ aryl; R ⁵ is CC ₁₂ alkyl, C ₄ -C ₁₀ aryl; X is Cl, Br, I, mesylate, tosylate or C ^ C ^ perfluoroalkyl sulfonate; m is a natural number, where 2 <m <y; n is a natural number, where 0 <n <ym; y is the number of free valences on the base A. 3. The method according to claim 2, characterized in that a compound of formula (la) is used as activated aromatics,

in which X is the same or different, Br, I or H and k, l, p, q, r, s are 0, 1, 2, 3, 4, with the proviso that at least two of the radicals X are Br or I. 4. The method according to one or more of the preceding claims, characterized in that one uses an amine component of the formula (II),

where the symbols have the following meanings: R ⁷ , R ⁸ are identical or different a) H; b) a straight-chain, branched or cyclic alkyl group having 1 to 22 carbon atoms, one or more CH ₂ groups being represented by -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -CR ¹ = CR ² , -O≡C-, SiR ³ R ⁴ , C ₄ -C ₁₀ aryldiyl, C ₄ -C ₁₀ heteroaryldiyl, cyclohexylene, -NR ⁵ -, where Heteroatoms must not be directly linked to one another, and one or more H atoms pass through F, Cl, Br can be replaced; wherein R ¹ to R ^{5 have} the meanings given in formula (I) in claim 2; c) a C ₄ -C ₁₂ aryl or heteroaryl group which can be substituted by one or more radicals R, where R has the same or different meanings given in formula (I) in claim 2. 5. The method according to one or more of the preceding claims, characterized in that one selects a ratio of activated group on the aromatic to amine of 1: 0.8 to 2, preferably 1: 1 to 1.5. 6. The method according to one or more of the preceding claims, characterized in that one uses a base from the group of alkali and alkaline earth metal hydroxides, alkali and alkaline earth metal carbonates, alkali metal bicarbonates, alkali and alkaline earth metal acetates, alkali and alkaline earth metal alcoholates and primary, secondary and tertiary amines . 7. The method according to one or more of the preceding claims, characterized in that the palladium component used is palladium metal, a palladium compound or a palladium complex which contains a phosphine ligand. 8. The method according to one or more of the preceding claims, characterized in that the palladium component in a proportion of 0.01 to 10 mol%, preferably 0.05 to 5 mol%, particularly preferably 0.1 to 3 mol% %, particularly preferably 0.1 to 1.5 mol%, based on the NH- Groups. 9. The method according to one or more of the preceding claims, characterized in that one uses a phosphine ligand from the group trialkylphosphines, tricycloalkylphosphines, triarylphosphines, where the three substituents on the phosphorus may be the same or different, chiral or achiral and one or more of the ligands the phosphorus groups of several Can link phosphines and part of this link can also be one or more metal atoms. 10. Use of aryl oligoamines, produced by a process according to one or more of claims 1 to 9, in electroluminescence devices, dye-sensitized photovoltaic cells and in xerography.